CN103619968A

CN103619968A - Ink and printing process

Info

Publication number: CN103619968A
Application number: CN201280022562.5A
Authority: CN
Inventors: 珍妮特·科特威尔; 玛丽·霍尔摩斯; 菲利普·道部尔; 阿杰伊·波帕特
Original assignee: Fujifilm Imaging Colorants Ltd
Current assignee: Fujifilm Imaging Colorants Ltd; Fujifilm Imaging Colorants Inc
Priority date: 2011-05-11
Filing date: 2012-05-08
Publication date: 2014-03-05
Also published as: TWI553063B; WO2012153119A1; US9309425B2; MX341323B; JP2014520171A; MX2013012973A; KR20140040743A; US20150035894A1; JP6026512B2; EP2707441A1; TW201302935A

Abstract

An ink comprising an encapsulated particulate solid and a liquid vehicle wherein: I) the encapsulated particulate solid comprises a particulate solid encapsulated with a cross-linked dispersant shell; and II) the ink comprises the components: a.from 0.1 to 20 parts of the encapsulated particulate solid; b.from 20 to 40 parts of glycerol; c.from 1 to 30 parts of ethylene glycol; d.from 0 to 20 parts of 2-pyrrolidone; e.from 0.01 to 3 parts of surfactant; f.from 0 to 10 parts of water-soluble polymer; g.from 0 to 20 parts of polymer particles; h.from 0 to 2 parts of biocide; i.from 20 to 75 parts of water; wherein all the parts are by weight and the sum of the components a. to i. is 100 parts.

Description

Ink and printing technique

Technical field

The present invention relates to ink, in particular to ink for ink-jet printer and the vessel that hold above-mentioned ink.The present invention also relates to use the printing technique (in particular to one way spray ink Printing technique) of above-mentioned ink.

Background technology

Family, office and many broad width ink jet printers are used scanning and printing head technology (scanning ink-jet printer).Scanning ink-jet printer is tending towards having relatively limited print speed.Therefore, scanning ink-jet printer can not be applicable to high-throughput commercial applications well.In scanning ink-jet printer, printing head moves (scanning) across substrate, and meanwhile, substrate is fixed.Along with printing head scanning is across substrate surface the width of substrate (conventionally across), thereby droplet of ink forms image towards substrate ejection.Conventionally, for obtaining optimum resolution or the highest print density, scanner head carries out Multiple-Scan to cover droplet of ink by the basal region to identical.The result of scan operation for forming the type belt of relative thin in substrate.Only at scanner head, form after the type belt of expectation, by print apparatus, move the substrate length direction of substrate (conventionally along), thereby can print another band.In this way, scanning ink-jet printer is printed required image lentamente.

Developed recently one way ink-jet printer.One way ink-jet printer provides higher print speed and in design, has considered the needs of high-throughput commercial applications.In one way spray ink Printing, one or more ink jetting heads are positioned at fixed position, and when substrate is advanced below printing head, substrate is printed conventionally in one way.In one way ink-jet printer, printer is large first watch, conventionally the same with substrate wide.

When with scanning ink-jet print over compared with time, one way spray ink Printing has more harsh requirement to ink-jet ink and tinting material.In scanning ink-jet printer, ink jetting head can clean repeatedly during the page print of substrate.On the contrary, in one way printer, head can not clean so continually.In addition, higher print speed and larger per minute ink discharge rate show that ink has to work extremely strong under one way printer mechanism.Therefore, ink-jet ink and the tinting material for one way ink-jet printer should desirably provide even higher levels of reliable operation at printer.

More specifically, ink for ink-jet printer and the tinting material for one way ink-jet printer should desirably provide:

I) long opening wide the time (good delay), thus even if make when nozzle for some time is during outage, ink component can not become dry on printer nozzle;

Ii) high stability, makes the particulate matter that does not have ink component to be tending towards flocculation, gathering, precipitation or produce oversized dimensions;

Iii) high light intensity (even in one way);

Iv) remarkable drop forms and drop dispersing characteristic, even in very short time scale or under high drop ejection frequency;

V) high reliability, when ink jet continues for some time through nozzle;

Once vi) print in substrate, drop relatively becomes dry fast;

Vii) good toxicology and use the volatile organic liquid of minimum quantity as far as possible;

Viii) low foaming character;

Ix) good photostabilization and image persistence;

X) remarkable ink storage stability;

Xi) the clear printing on highly porous medium (such as ripple substrate).

The substrate that the common utilization of one way ink-jet printer is very different from the printer of family and office.Home printer can be used expensive substrate (such as high-quality printing paper) well.Printing paper has the microvoid structure of high whiteness, high glossiness and high controllability conventionally, and it is specially adapted to controlled extension and the infiltration of ink-jet ink.For one way spray ink Printing, it is more cheap that substrate is tending towards, and coating (if having) is tending towards not being applicable to so absorb ink-jet ink.For these substrates, known ink-jet ink is tending towards being penetrated into too far in substrate conventionally, causes loss, wicking action and/or the print through of optical density(OD).

Ink based on pigment comprises the pigment particle being dispersed in ink, yet the ink based on dyestuff comprises the dyestuff being dissolved in ink.Ink based on pigment is tending towards having some advantages in some applications.For example, the light of the ink based on pigment and ozone fastness are tending towards being better than the ink based on dyestuff.

That is to say, if ink is ink rather than the ink based on dyestuff based on pigment, meeting many demand even can be more difficult.For example, well-known, in the ink based on pigment, thereby pigment particle can be tending towards the particulate of cohesion or flocculation generation oversized dimensions along with the time, and the particulate of these oversized dimensions can block or damage the printing of small spray ink Printing machine nozzle.Meanwhile, well-known, if ink comprises the organic liquid of higher relative quantity or the tensio-active agent of strong absorption, the ink based on pigment is tending towards flocculation conventionally.Therefore, in many aspects in, compare with the ink based on pigment, the ink based on dyestuff is more suitable for the high printer reliability requirement of printing in one way.

In our research, we find that meet many or all the demand is difficults simultaneously.Some demands that are difficult to especially simultaneously realize are high colloidal stability and the high printer reliability of high light intensity, the ink based on pigment.

prior art

PCT patent publication WO2005/080513 discloses the ink-jet ink that comprises glycerol.This patent publication is not mentioned pigment, one way spray ink Printing or the ripple substrate of sealing.

Summary of the invention

definition

Unless otherwise prescribed, otherwise show and comprise may having more than one such as the vocabulary of " ".For example, the granular solids that " " seals also comprises having the more than one granular solids of sealing.

In the present invention, except as otherwise noted, all umbers all by weight.

detailed description of the present invention

first aspect

According to a first aspect of the invention, provide and comprised the granular solids sealed and the ink of liquid medium, wherein:

I) granular solids of sealing comprises the granular solids that uses crosslinked dispersion agent shell enclosure; And

II) ink comprises following component:

The granular solids of sealing of a.0.1 to 20 part;

The glycerol of b.15 to 60 part;

The ethylene glycol of c.1 to 30 part;

The 2-Pyrrolidone of d.0 to 20 part;

The tensio-active agent of e.0.01 to 3 part;

The water-soluble polymers of f.0 to 10 part;

The polymer particles of g.0 to 20 part;

The biocide of h.0 to 2 part;

The water of i.20 to 75 part;

Wherein, all umbers are all calculated by weight, and the umber sum of component a. to i. is 100 parts.

Meanwhile, component a's to i adds and is 100 parts and be not illustrated in and in ink, do not have other ink component.Ink comprises component a to i, and other ink component also can exist accordingly.

Component a and g are generally the form of dispersion.Component e, f and h are generally solution.The umber of component a, e, f, g and h is to consider on the basis of solid.Therefore, for example, 10 parts of solid contents are 10%(weight) polymer emulsion be 1 part of (weight) polymer particles.Similarly, 20 parts of solid contents are 15%(weight) the granular solids dispersion of sealing be 3 parts of granular solids that (weight) is sealed.As another example, 1 part of 50%(weight) antimicrobial agent solution is considered to 0.5 portion of biocide.

A. the granular solids of sealing

Preferably, the granular solids of sealing has the particle size that is less than 1 micron, and preferred diameter is 30 to 500nm, and further preferred diameter is 50 to 300nm, and particularly preferred diameter is 70 to 200nm.

Preferably, average particle diameter is the equal diameter of Z.Preferably, mean particle dia is measured by for example laser scattering method.For the suitable instrument of measuring, comprise the instrument of being sold by Ma Erwen (Malvern) and Ku Erte (Coulter).Preferred equipment is Malvern Zetasizer ^tM.

In our research, we find that the granular solids of sealing using in the present invention provides the ink with good optical, the granular solids of sealing has stability in the ink with a large amount of glycerol and ethylene glycol, and in ink-jet printer and one way ink-jet printer, the granular solids of sealing helps ink to print extremely reliably.When glycerol is used together with ethylene glycol, for the preparation of the dispersion agent of the granular solids of sealing, also provide remarkable rheological, drop to form and drop dispersing characteristic.Simultaneously, be reluctant to be confined to any concrete theory, can be sure of, the granular solids of sealing according to a first aspect of the invention, for the preparation of the dispersion agent of the granular solids of sealing and one way printer mechanism mutually synergy so that gratifying especially ink jet and print performance characteristic to be provided.

the preparation of the granular solids of sealing

Preferably, the granular solids of sealing by being included in the technique preparation of crosslinked dispersion agent under the existence of granular solids and liquid medium.

The amount of the granular solids of sealing in ink is preferably 0.1 to 20 part (weight), is more preferably 0.1 to 15 part (weight), further preferably 0.1 to 10 part (weight) and particularly preferred be 1 to 10 part (weight).

granular solids

Granular solids can be unrestricted any type.Preferably, granular solids is insoluble to ink substantially.Substantially the insoluble solubleness being illustrated in ink is less than 1%(weight), the preferred 0.1%(weight that is less than).Preferably, at the temperature of 25 ℃, measure solubleness.Preferably, under the condition that is 8 at pH, measure solubleness.It is that 25 ℃ and pH are adjusted to 8 the mixture that comprises 18 parts of ethylene glycol, 30 parts of glycerol, 5 parts of pyrrolidone and 46 parts of water that preferred granular solids is insoluble to temperature.

Preferably, granular solids for or comprise tinting material, more preferably granular solids for or comprise pigment.

Pigment can be organism or inorganics.

Preferred granular solids is pigment dyestuff, for example, third edition Colour Index (1971) (the Third Edition of the Colour Index (1971)) with and subsequent revised edition and its supplementary issue in name be called the described all types of pigment of chapters and sections of " pigment ".The example of pigment dyestuff is azo (comprising tetrazo and condensation azo), thioindigo, indanthrone, different indanthrone (isoindanthrone), anthanthrone, anthraquinone, isoviolanthrone, three thiophene dioxazines (triphendioxazine), quinacridone, and phthalocyanine series, particularly copper phthalocyanine and its core halo derivatives, and can be also the color lake of acid, alkali and mordanting dye.Preferred pigment dyestuff is phthalocyanine, particularly copper phthalocyanine, azo pigment, indanthrone and anthanthrone, quinacridone.

Preferred mineral dye comprises: metal oxide, sulfide, nitride and carbide (for example, titanium dioxide and silicon-dioxide), metallic pigment (for example, kaolin) and particularly carbon black.For these pigment, carbon black is particularly preferred.

Preferred carbon black is channel black, the trade mark Nipex by name particularly being sold by Evonik ^rTMchannel black.

The in the situation that of charcoal blacks, by a kind of like this method, prepare charcoal blacks, make some carbon blacksurfaces there is the group (for example, carboxylic acid and/or oh group) of oxidation.Yet the amount of these groups preferably can not be too high, if may being distributed in water in the situation that not having dispersion agent to help, (can not certainly disperse) too high pigment.

Preferably, in the situation that not having dispersion agent to help, pigment can not be distributed in water-based liquid medium (particularly pure water), that is, need to exist dispersion agent to help dispersion.Preferably, pigment does not pass through chemical surface treatment, for example, has and is covalently bound to its surperficial ionic group and (is not especially-CO ₂h or-SO ₃h).

Preferably, pigment is blue-greenish colour, magenta, yellow or black pigment.

Can use more than a kind of pigment in the present invention.

For the setting of printing color ink, pigment optimization is carbon black, C.I. pigment Blue 15: 3, C.I. pigment red 122 and C.I. Pigment Yellow 73 74.

Preferably, before crosslinked, granular solids is pulverized (for example, milling) under the condition of liquid (being preferably the liquid that comprises water) and dispersion agent existence.About pulverizing, we preferably mean those technique that has reduced significantly the particle size of granular solids.The example of breaking method comprises Micro Fluid method, high pressure homogenizing method, sonioation method and grinding method (particularly pearl mill method).Preferably, the dispersion agent existing during pulverising step only has those crosslinked to seal the linking agent of granular solids subsequently.This makes any (non-encapsulated) freely dispersion agent drop to minimum.Preferably, with respect to the granular solids of 100 parts (weight), the dispersion agent of existence is 5 to 100 parts (weight), be more preferably 10 to 80 parts (weight) and particularly preferred be 20 to 50 parts (weight).

After pulverizing, granular solids preferably has the particle size that is less than 1 micron, and preferred diameter is 30 to 500nm, further preferred diameter be 50 to 300nm and particularly preferred diameter be 70 to 200nm.

The equal diameter of the preferred Z of average particle diameter.Preferably by for example laser scattering method, measure mean particle dia.For the suitable instrument of measuring, comprise the instrument of being sold by Ma Erwen (Malvern) and Ku Erte (Coulter).Preferred equipment is Malvern Zetasizer ^tM.

dispersion agent

Preferably, dispersion agent is polymkeric substance.

Preferably, the number-average molecular weight of dispersion agent is 1000 to 1000000, is more preferably 5000 to 100000 and particularly preferably 20000 to 80000.Preferably by gel permeation chromatography, measure molecular weight.Preferably, the solvent for GPC is water, tetrahydrofuran (THF) or dimethyl formamide.Preferably, by known polystyrene or the method calibration molecular weight of polyoxyethylene glycol standard specimen more specifically.

Preferably, polymeric dispersant for or comprise polyester, urethane, polyethers, polystyrene, poly-(methyl) acrylate or their grafting and physical combination.In these, poly-(methyl) acrylate is preferred.

Preferably, by copolymerization component i at least) and ii) obtain and maybe can obtain polymeric dispersant:

I) one or more (methyl) acrylate monomers all without ionic group of 70 to 95 parts;

Ii) one or more (methyl) acrylate monomers all with at least one ionic group of 5 to 30 parts;

Wherein, component i) and umber sum be ii) 100, and all umbers are all by weight.

More preferably, by least copolymerization component i) to iii) obtaining and maybe can obtain polymeric dispersant:

Iii) be no more than one or more unsaturated vinyl monomers all with polyethyleneoxy group of 20 parts (weight);

Wherein, component i) to umber sum be iii) 100, and all umbers are all by weight.

Preferably, polymeric dispersant comprises or is comprised of the repeating unit of (methyl) acrylate monomer.

component i) monomer in

Preferably, component i) comprise at least 40 parts (weight), being more preferably at least 45 parts (weight), is further preferably at least 50 parts (weight), the benzyl methacrylate of particularly preferably at least 60 parts (weight) and more particularly preferably at least 70 parts (weight).Preferably, component i) only by benzyl methacrylate, formed.We find, the amount that increases benzyl methacrylate provides improved ink performance, such as the printer reliability in optical density(OD), one way printer and the colloidal stability in ink.

In the situation that component i) comprise benzyl methacrylate monomer in addition, it preferably includes (methyl) vinylformic acid C _1-20hydrocarbon ester.Preferably, C _1-20alkyl is alkyl group.Alkyl group can be line style or branched chain type.Preferred example comprises (methyl) butyl acrylate, (methyl) Octyl acrylate, (methyl) ethyl acrylate, (methyl) methyl acrylate, isobornyl acrylate, dodecyl acrylate and octadecyl acrylate.

Preferably, component i) be 70 parts (weight) to 92 parts (weight), be more preferably 70 parts (weight) to 90 parts (weight) and particularly preferably 75 parts (weight) to 85 parts (weight).

the monomer of component in ii)

Preferably, the ionic group in the monomer of component in is ii) negatively charged ion.The preferred embodiment of anionic group comprises phosphorous acidic-group (phosphonic acids with phosphorous), sulfonic acid group, and is hydroxy-acid group especially.Preferably, component each (methyl) acrylate monomer in ii) has 1 to 3, more preferably has 1 or 2 and especially only have an ionic group.

The preferred embodiment with (methyl) acrylate monomer of hydroxy-acid group comprises methylene-succinic acid, fumaric acid, toxilic acid, β-crotonic acid, beta carboxy ethyl acrylate, vinylformic acid and methacrylic acid in particular.Preferably component ii) comprises methacrylic acid, and more preferably component ii) only comprises methacrylic acid.

Preferably, component be ii) 8 parts (weight) to 30 parts (weight), be more preferably 10 parts (weight) to 30 parts (weight) and be that 15 parts (weight) are to 25 parts (weight) especially.

the monomer of component in iii)

In increasing progressively priority, component is iii) for being no more than the unsaturated vinyl monomer all with polyethyleneoxy group of 10 parts, 5 parts, 2 parts, 1 part, 0.5 part and 0 part.For unsaturated vinyl monomer, we preferably mean C=C.For object of the present invention, if monomer belongs to component i) and iii) or component ii) and iii), this monomer belongs to component iii).Therefore, do not consider other groups, the unsaturated vinyl monomer with polyethyleneoxy group be always included in component iii) in.

For polyethyleneoxy group, we mean any for or comprise (CH ₂cH ₂o) _n-group, wherein n be 2 or more than.The terminal group of polyethylene oxygen chain can be any type.Therefore the quantity of unsaturated vinyl monomer that, has a polyethyleneoxy group of alkyl, aryl, heterocycle and H end-blocking is also subject to component restriction iii).

When any monomer be present in component iii) in time, the unsaturated vinyl monomer with polyethyleneoxy group is preferably (methyl) acrylate.

We find, at component iii) in the low amount requirement of the monomer for these kinds of expressing cause providing the granular solids of sealing of the printer reliability in improved optical density(OD), stability and one way ink-jet printer.

optional monomer

Except component i) to those monomers in iii), can also there is extraly optional monomer.

Alternatively, the component of copolymerization comprises and is no more than 50 parts (weight), more preferably be no more than 20 parts (weight), what be particularly preferably no more than 10 parts (weight) and be more particularly no more than 5 parts (weight) is different from component i) to the optional monomer of those monomers of mentioning in iii).Particularly preferably, by copolymerization only by component i) maybe can obtain polymkeric substance to the component acquisition iii) forming.

preferred polymeric dispersant

Consider content above, by copolymerization component i at least) to iii) obtaining and maybe can obtain preferred polymeric dispersant:

I) one or more (methyl) acrylate monomers all without ionic group of 70 to 95 parts, it comprises at least 40 parts of benzyl methacrylates;

Ii) the methacrylic acid of 5 to 30 parts;

Iii) being no more than 5 parts, is more preferably one or more unsaturated vinyl monomers all with polyethyleneoxy group of 0 part;

Wherein, i) to umber sum be iii) 100, and all umber is by weight.

Further preferably, by copolymerization component i at least) to iii) obtaining and maybe can obtain polymeric dispersant:

I) benzyl methacrylate of 70 to 95 parts;

Ii) the methacrylic acid of 5 to 30 parts;

Wherein, i) to umber sum be iii) 100, and all umber is by weight.

In these polymeric dispersants, preferably, except component i) to those monomers of mentioning in iii), there is no other monomers.

dispersion agent preparation

Can prepare dispersion agent by the polymerization process of any type, and have no particular limits.Can use the method for letex polymerization, mass polymerization, suspension polymerization and particularly solution polymerization.The initiator using in polymerization can or be more preferably radical initiator for cationic initiator, anionic initiator.Can in the situation that existing, implement by chain-transfer agent polymerization, thus restriction molecule amount.

crosslinked

Preferably, crosslinked dispersion agent in the situation that of granular solids and liquid medium existence, thereby the granular solids that preparation is sealed.

Can be by the dispersion agent of use self-crosslinkable or by using the combination of dispersion agent and linking agent to realize crosslinking reaction.

Can adopt any suitable cross-linking chemistry agent.In the 6th page table 1 of suitable cross-linking chemistry agent in PCT patent publication WO2005/061087, be described.Preferably, by using epoxy crosslinking agent to realize crosslinking reaction.

We find, by the crosslinking reaction cross-linked polymer dispersion agent shell between carboxylic acid and epoxide group, are preferred.We find, this scheme is the scheme that is especially effectively cross-linked, and it is unstable that this scheme can not trend towards the granular solids that makes to be distributed in liquid medium.Preferably, hydroxy-acid group is present in dispersion agent, and epoxide adds as linking agent.

Low temperature is preferred for being cross-linked, because this causes flocculation and the particle size growth of the lower level of granular solids in liquid medium.Preferably, the enforcement temperature of crosslinking reaction is 10 ℃ to 90 ℃ and is more preferably 30 ℃ to 70 ℃.

The pH of crosslinking reaction is preferably 7 to 14, be more preferably 7 to 12 and particularly preferred be 8 to 11.

In crosslinking reaction process, preferably there is borate compound.We find, this has improved the efficiency of crosslinking reaction.

Borate compound preferably includes boric acid, metaboric acid, tetraboric acid or pyroboric acid, or their combination, or their salt.

The time of crosslinking reaction is somewhat dependent upon temperature and pH.Yet the preferred time is 1 to 24 hour, is more preferably 1 to 8 hour.

liquid medium

In the present invention, the liquid medium that uses refers to the liquid ingredient existing in the preparation process of the granular solids of sealing.Liquid ingredient in final ink is called liquid medium.

Liquid medium is preferably polarity.

The example of suitable polar liquid medium comprises ethers, glycols, alcohols, polyalcohols, amides, ketone, and is water especially.

Preferably, liquid medium is or comprises water, because this is tending towards producing stable especially and the good granular solids of sealing.Preferably, liquid medium comprises the weight from 1%() to 100%(weight), more preferably comprise the weight from 10%() to 100%(weight), comprise especially the weight from 30%() to 100%(weight), more particularly comprise the weight from 50%() to 100%(weight), especially especially comprise the weight from 60%() to 100%(weight), and comprise the most especially the weight from 80%() to 100%(weight) water.Remainder is one or more polar organic liquids preferably.In some cases, preferably liquid medium comprises and water and be less than 5% is more preferably less than 2%, is less than especially 1% and be 0% organic liquid the most especially.The liquid medium that almost only comprises water forms to offer the best to ink and selects and environmental friendliness more.

When liquid medium comprises more than a kind of liquid, described liquid medium can be the form (for example, liquid-liquid emulsion) of multi-phase fluid, but is preferably the form of single-phase (homogeneous phase) liquid.

Preferably, the polar liquid outside dewatering is water miscible.

In one case, liquid medium comprises water and water miscible organic liquid.Due to the use that this liquid medium helps to dissolve and/or disperses linking agent widely and be convenient to more hydrophobic dispersants, therefore this liquid medium is useful.

The preferred water miscible organic liquid being included in liquid medium comprises:

I) C _1-6alkanol, is preferably methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, cyclopentanol and hexalin;

Ii) linear acid amides, is preferably dimethyl formamide or N,N-DIMETHYLACETAMIDE;

Iii) ethers, is preferably tetrahydrofuran (THF) and dioxane;

Iv) glycols, be preferably the glycol with 2 to 12 carbon atoms, for example, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol and thiodiglycol, and oligo alkylene glycols and polyalkylene glycol, be preferably glycol ether, triglycol, polyoxyethylene glycol and polypropylene glycol;

V) three alcohols, are preferably glycerol and 1,2,6-hexanetriol;

Vi) the ethers of glycol, is preferably single C of the glycol with 2-12 carbon atom _1-4alkyl oxide is 2-ethylene glycol monomethyl ether, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy)-ethanol, 2-[2-(2-methoxy ethoxy) oxyethyl group especially] ethanol, 2-[2-(2-ethoxy ethoxy)-oxyethyl group]-ethanol and ethylene glycol monoallyl ether;

Vii) cyclic amide class, is preferably 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, hexanolactam and 1,3-dimethyl-imidazolinone.

In some cases, liquid medium comprise water and 1 part or more than, be the water miscible organic liquid of 1 part to 8 parts especially.

According to a first aspect of the invention, under many circumstances, before preparation ink, preferably from the dispersion system of the granular solids sealed, remove all organic liquids.

Can be by comprising the method for distillation, segregation and redispersion or more preferably having cleaned this removal by film.

the purifying of the granular solids of sealing

Preferably, before preparation ink, the granular solids of sealing is carried out to purifying.Preferably, the basic impurity of removing such as unwanted non-encapsulated dispersion agent freely, untapped linking agent and borate material (when existing).Preferred purification process comprises filtration washing, and especially for film is processed.

B. glycerol

Glycerol is also to comprise that other popular names behaviours of glycerine (glycerine and glycerin) are known.Formal IUPAC name is called 1,2,3-Glycerin.

Preferably, in ink, the amount of glycerol is that 15 parts (weight) are to 50 parts (weight), be more preferably that 15 parts (weight) are to 40 parts (weight), especially be more preferably 17 parts (weight) to 40 parts (weight), be 20 parts (weight) to 40 parts (weight) and be more particularly that 25 parts (weight) are to 35 parts (weight) especially.In particularly preferred situation, in ink, the amount of glycerol is 30+/-2 part (weight).In many cases, preferably, the amount of glycerol is at least 17 parts (weight).

C. ethylene glycol

Ethylene glycol is also known with simpler title glycol behaviour.Formal IUPAC name is called 1,2-dihydroxyl ethane.

Preferably, in ink, the amount of ethylene glycol is that 5 parts (weight) are to 30 parts (weight), be more preferably 5 parts (weight) to 25 parts (weight), be especially more preferably 7 parts (weight) to 25 parts (weight) and be that 10 parts (weight) are to 25 parts (weight) especially.In particularly preferred situation, in ink, the amount of ethylene glycol is 18+/-2 part (weight).In many cases, preferably, the amount of ethylene glycol is at least 7 parts (weight).

D. 2-Pyrrolidone

2-Pyrrolidone (in this example, this is formal IUPAC title) is not called 2-Pyrrolidone (2-Pyrrolidinone) or 2-pyrroles (2-Pyrol) so conventionally yet.

Preferably, in ink, the amount of 2-Pyrrolidone is that 0.1 part (weight) is to 20 parts (weight), be more preferably 1 part (weight) to 15 parts (weight), be especially 1 part (weight) to 10 parts (weight), be more particularly that 2.5 parts (weight) are to 7.5 parts (weight).In some cases, the amount of the 2-Pyrrolidone in ink be 0 part (weight) to 20 parts (weight), be more preferably that 0 part (weight) is to 10 parts (weight).

E. tensio-active agent

In ink, the amount of tensio-active agent is preferably 0.1 part (weight) to 2 parts (weight), be more preferably that 0.1 part (weight) is to 1.5 parts (weight), especially being preferably 0.15 part (weight) to 1.5 parts (weight), is that 0.5 part (weight) is to 1.5 parts (weight) especially.In particularly preferred situation, in ink, the amount of tensio-active agent is 0.8+/-0.2 part (weight).In other cases, the amount of tensio-active agent is 0.4+ part/-0.2 part (weight).

Tensio-active agent can be for any kind and without any special restriction.(the thering is hydrophobic grouping and hydrophilic radical) that preferred tensio-active agent is both sexes.Preferred hydrophilic radical is sulfonic acid group, phosphonyl group, hydroxy-acid group and vinyloxy group group.Preferred hydrophobic grouping is aromatic yl group, alkyl group, propenyloxy group group and butenyloxy group, and their combination.

The tensio-active agent (being 2,4,7,9-tetramethyl--5-decine-4 especially, 7-glycol and corresponding ethoxy compound) preferably with alkyne diol structure.Preferred example comprises the trade mark of being sold by air products company (Air Products) Surfynol by name ^tMtensio-active agent, and be Surfynol especially ^tM465,104E and 440.In these tensio-active agents, Surfynol ^tM104E is preferred, and it is 2,4,7,9-tetramethyl--5-decine-4,7-glycol (CAS code is 126-86-3).

Can use one or more of these tensio-active agents.

We find, when when glycerol is used in combination together with ethylene glycol, these tensio-active agents a large amount of and preferred type provide remarkable droplet jet and dispersing characteristic, and these characteristics are particularly importants for spray ink Printing and particularly one way spray ink Printing.These preferred alkyne diol tensio-active agents are also achieved one's goal and are provided low foaming tendency to ink.

The process of spray ink Printing is dynamic process, and wherein, the surface of ink is constantly disturbed.In this environment, the surface tension of the ink in the low-down surface time is significant and can affects dropleting speed, required voltage, retardance, print quality and optical density(OD).When ink formulation, the type of careful option table surface-active agent, mobility and amount are desirable, to provide better drop to form and spray characteristic to ink.

F. water-soluble polymers

For clear, when polymkeric substance is water miscible and is tensio-active agent, it is considered to tensio-active agent (component e.) in this article.

Water-soluble polymers can and have no particular limits for any type.Word used herein " water-soluble " is included in has at least 5%(weight in water) the polymkeric substance of solubleness.Preferably, water is distilled water.Preferably, any acidic-group in polymkeric substance neutralizes with sodium hydroxide, and any basic group in polymkeric substance neutralizes with acetic acid.Preferably, the acidity based on existing or the stoichiometry of basic group, neutralization is 100%.Preferably, under the condition of 25 ℃, measure solubleness.Thereby soluble polymkeric substance is tending towards dissolving complete (or almost completely) limpid polymers soln of formation in water.

The example of suitable water-soluble polymers comprises polymkeric substance (for example polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone), polyester, urethane, the Mierocrystalline cellulose of unsaturated vinyl monomer, and is polyoxyethylene glycol (being sometimes referred to as polyoxyethylene) especially.

Preferably, water-soluble polymers for or comprise polyoxyethylene glycol.

Preferably, the molecular weight of water-soluble polymers is 150 to 200000, is more preferably 1000 to 100000; Especially be preferably 5000 to 50000, and be 10000 to 30000 especially.In one case, water-soluble polymers preferably has 30000 to 40000 molecular weight.Preferably molecular weight is by the definite number-average molecular weight of gel permeation chromatography.

Preferably, in ink, the amount of water-soluble polymers is no more than 7 parts (weight), more preferably for being no more than 5 parts (weight), and more particularly for being no more than 3 parts (weight).In some cases, expectation be that the amount of water-soluble polymers in ink is at least 0.1 part (weight), be more preferably at least 0.2 part (weight).

The preferred amount of water-soluble polymers be 0.01 part (weight) to 7 parts (weight), be more preferably 0.05 part (weight) to 5 parts (weight), be that 0.1 part (weight) is to 3 parts (weight) especially.

Meanwhile, be reluctant to be confined to any concrete theory, it is believed that, water-soluble polymers and be tending towards assist adjusting especially the rheological of ink for polyoxyethylene glycol, thus promote good especially ink-jet ejection (firing) and print.

In some cases, can use two or more different water-soluble polymerss, particularly two or more different polyoxyethylene glycol.Preferably, two or more polyoxyethylene glycol have different molecular weight.Preferably, a kind of molecular weight of polyoxyethylene glycol is 1000 to 50000, and the molecular weight of another kind of polyoxyethylene glycol is 150 to 999.

In some cases, can be advantageously, component f. comprises the water-soluble polymers that is different from polyoxyethylene glycol.In some cases, component f. comprises water-soluble polymers and the polyoxyethylene glycol that is different from polyoxyethylene glycol.The water-soluble polymers that is preferably different from polyoxyethylene glycol comprises polyester, by the polymkeric substance of unsaturated vinyl monomer polymerization and be urethane especially.

For clear, water-soluble polymers is not sealed granular solids, can not be in office where face serves as dispersion agent.

G. polymer particles

Ink can comprise polymer particles alternatively.Can use the polymer particles of any kind and not restriction.When there is polymer particles, it is separated from the granular solids of sealing and is different with the granular solids of sealing.Polymkeric substance in polymer particles can, for multipolymer, polyester, polyethers, urethane, polycarbonate or the polymeric amide of polystyrene, poly-(methyl) vinylformic acid, vinylbenzene-methacrylic acid, comprise the polymkeric substance of grafting and their physical mixture.Polymkeric substance can be also natural polymer, such as Mierocrystalline cellulose, protein or wax.

Preferably, the average particle diameter of polymer particles is no more than 1 micron, is more preferably 10 to 500nm, is 30 to 200nm especially, and is 30 to 150nm the most especially.For determining that the preferred method of the particle size of polymer particles is photon correlation spectroscopy.

When there is polymer particles, it can be for helping the combination of granular solids and substrate, or help to improve the glossiness of final printing.In typical dilution method, polymer particles is tending towards the almost not impact of the rheological of ink.

Especially, preferred polymer particles is those polymer particles of preparing by polymerization of vinyl unsaturated monomer (being acrylate, methacrylic ester, vinylbenzene etc. especially).Other useful polymer particles comprise polyester and urethane.In water, polymer particles is tending towards having the solubleness that is less than 5%, more preferably for being less than 1%(weight), use with above in the identical method measurement for water-soluble polymers mentioned.

We find, exist a large amount of polymer particles can be unfavorable to the operability of ink-jet and retardance.Therefore, preferably, in ink, the amount of polymer particles is no more than 15 parts (weight), is more preferably no more than 12 parts (weight), is no more than especially 10 parts (weight), is more particularly no more than 5 parts (weight), and is no more than the most especially 3 parts (weight).In some cases, in ink the amount of polymer particles be 0.1 part (weight) to 15 parts (weight), be more preferably 1 part (weight) to 12 parts (weight), and be that 3 parts (weight) are to 10 parts (weight) especially.We find, these a large amount of polymer particles are tending towards improving adhesion property and the wet fastness properties that is printed on suprabasil final ink.

In some cases, preferably, in ink, there is not polymer particles.Certainly, when dispersion agent is polymkeric substance, word polymer particles does not mean the granular solids of sealing.

Can manufacture polymer particles by many possible methods, possible method comprises Solution Dispersion polymerization, melting dispersion copolymerization method, suspension polymerization, and is emulsion polymerization especially.

Tensio-active agent by absorption and/or as the water-dispersion group of the part of micro polymer kernel structure, polymer particles can be colloid-stabilised.

H. biocide

Ink can comprise the mixture of biocide or multiple biocide alternatively.

Can use arbitrarily biocide and without any specific restriction.We find, BIT is the specially suitable biocide for ink of the present invention, and BIT can be used as Proxel ^tMgXL business is bought.In ink, the amount of biocide is preferably and is no more than 1.5 parts (weight), especially for being no more than 1 part (weight).

In ink, the amount of biocide is preferably 0.0001 part (weight) to 1.5 parts (weight), be more preferably 0.01 part (weight) to 1 part (weight), be that 0.01 part (weight) is to 0.3 part (weight) especially.

I. water

The amount of the water in ink is preferably 25 parts (weight) to 70 parts (weight), be more preferably that 30 parts (weight) are to 60 parts (weight), be especially 35 parts (weight) to 55 parts (weight), and be more particularly that 40 parts (weight) are to 55 parts (weight).In the preferred case, in ink, the amount of water is 46+/-2 part (weight).

Before in being formulated into ink, preferably water is carried out to purifying.Preferably, by contacting with deionization resin, the method purified water of distillation and/or reverse osmosis.

J. optional ink component

Ink can comprise the ink component except component a. to i. alternatively.

The example of suitable optional ink component comprises:

Metal chelator; Fouling (kogation) inhibitor; The rheology modifier that is different from water-soluble polymers, dyestuff; Further dispersion agent, water-soluble organic liquid (being different from glycerol, ethylene glycol and 2-Pyrrolidone); Non-encapsulated granular solids (for example, pigment), defoamer; Alkali and damping fluid etc.

Preferably, ink comprises and is no more than 10 parts (weight), more preferably for being no more than 5 parts (weight), and especially for being no more than all optional ink component in ink that are present in of 3 parts (weight).

Preferably, except crosslinked, to seal the dispersion agent of granular solids, ink does not comprise dispersion agent.

preferred ink component

Preferably, components b, c and d amount at least 30 parts (weight), are more preferably at least 35 parts (weight), are more particularly at least 40 parts (weight).

According to above preferably, preferred ink comprises following component:

A.0.1 part to the granular solids of sealing of 10 parts;

B.20 part to the glycerol of 40 parts;

C.5 part to the ethylene glycol of 25 parts;

D.0 part to the 2-Pyrrolidone of 10 parts;

E.0.1 part to the tensio-active agent of 2 parts;

F.0 part to the polyoxyethylene glycol of 5 parts;

G.0 part to the polymer particles of 15 parts;

H.0 part to the biocide of 1 part;

I.35 part to the water of 55 parts;

Wherein, all by weight, and the umber of component a to i adds all umbers and be 100.

We find, these ink can pass through ink-jet printer and particularly one way ink-jet printer and print especially reliably.In addition, these ink can be printed effectively in corrugated substrate and newsprint substrate.

ink characteristics

Preferably, ink is ink-jet ink (that is, can by the ink of printing of inkjet printer).

Following ink requires to provide the ink that is specially adapted to spray ink Printing and one way spray ink Printing.

The pH of ink is according to a first aspect of the invention preferably and is equal to or greater than 7, is more preferably 7 to 12, and is 8 to 11 especially.Preferably, for sealing the dispersion agent of granular solids, with alkali, neutralize.Alkali can be alkali-metal oxyhydroxide, organic amine, alkanolamine or ammonia.Therefore, any ion (the being preferably acidity) group in dispersion agent can be the form of salt, free acid or free alkali.

Preferably, the surface tension of ink is 20mN/m to 50mN/m, is more preferably 20mN/m to 40mN/m, and is 25mN/m to 35mN/m especially.Preferably, by Kibron Aquapi tensiometer measurement device surface tension.Preferably, at the temperature of 25 ℃, measure the surface tension of ink.

Preferably, by strainer, filter ink, the mean pore size of strainer is no more than 5 microns, more preferably for being no more than 2 microns, and especially for being no more than 1 micron.

Preferably, while measuring under the condition at 30 ℃, the viscosity of ink is no more than 50mPa.s, more preferably for being no more than 30mPa.s, and especially for being no more than 20mPa.s.For the preferred device of measuring viscosity, be Brookfield DV II viscosity apparatus, preferably use rotor numbers 0 or 18.Preferred viscosity for ink is 1mPa.s to 20mPa.s, is more preferably 2mPa.s to 17mPa.s, and is 3mPa.s to 15mPa.s especially.

Preferably, ink comprises and is less than 500ppm, more preferably for being less than 250ppm, and especially for being less than multivalent (divalence or higher valent) metal ion of 100ppm.Ppm used herein means millionth umber (weight).

ink preparation method

Can and use device or the method for any appropriate that ink component is admixed together by order arbitrarily.Preferably, the granular solids of sealing mixes with the form of disperseing in water with other compositions.

Preferred method for the preparation of ink comprises the following steps:

I) add together tensio-active agent and ethylene glycol to form surfactant soln;

Ii) other ink component the granular solids except sealing are joined to step I) in the surfactant soln that forms, to form liquid medium;

Iii) by step I i) in the liquid medium that forms join in the aqueous dispersion of the granular solids of sealing.

Preferably, in the time of mixed ink component, implement whole step I) extremely iii).Suitable mixing tank is paddle stirrer or pressure-even pulp crusher.

second aspect

According to a second aspect of the invention, provide for ink print is according to a first aspect of the invention arrived to suprabasil technique.

spray ink Printing

Preferably, printer is ink-jet printer, and is one way ink-jet printer especially.Preferably, by the mode of ink-jet printer, implement to print.Preferably, one way ink-jet printer has one or more ink jet-print heads, and ink jet-print head extends the whole width across print zone individually or in combination.Print zone can be wider than 2.5cm, 5cm, 10cm, 20cm, 50cm, 100cm etc.In fact, in some printers, print zone is wider than 1m, 1.5m or is even wider than 2m.Preferably, use one way ink-jet printer in one way, to implement to print.

Ink-jet printer can use piezoelectric type head, hot type head or voice-control head ink jet drop.

substrate

Ink of the present invention is applicable to large-scale substrate conventionally, such as paper, textiles, glass, pottery, metal and plastic-substrates.

That is to say, ink of the present invention is specially adapted to perforated substrate.In these perforated substrates, most preferred is the perforated substrate that comprises paper.

Preferred a kind of substrate is ripple substrate (also referred to as corrugated paper).Compare with many substrates, due to the good nature of himself, ripple substrate is tending towards thicker and has every square metre of higher quality.The quality of preferred ripple substrate is 40g/m ²to 800g/m ², be more preferably 100g/m ²to 800g/m ², and be 200g/m especially ²to 800g/m ².Term ripple used herein substrate preferably means to comprise those paper substrates with corrugated paper.Ripple substrate can have (and preferably) one, two and or a plurality of liner board.Ripple substrate can be individual layer or the liner board multilayer between corrugated ply of paper alternatively.

Although ink can be printed on corrugated surface, be preferably printed on smooth paper liner board.

Ink is particularly suitable for having porous surface and quality is 40g/m ²to 800g/m ²substrate.

Ripple substrate is tending towards high-absorbable, and has mode by spray ink Printing and form high-quality printing thereon and be tending towards the surface of difficulty especially.The particular problem of printing in ripple substrate is wicking action, and wherein, thereby ink is tending towards extending on surface reduction picture quality.It is too dark that another problem is that ink can infiltrate through ripple substrate, and therefore, impression shows lower optical densities in surface.We find, ink of the present invention provides good balance of properties, and character comprises good optical density(OD) and picture quality (or even in ripple substrate).The more difficult printing that realizes high light intensity while implementing to print in one way.In this system, more ink layeies are not applied to the chance subsequently on print zone again.

Another preferred substrate is newsprinting paper.Newsprinting paper is the substrate that comprises porous paper.The generally planar single page of newsprinting paper (different from ripple substrate).Compare with ripple substrate, newsprinting paper is tending towards having significantly every square metre of lower quality.The quality of preferred newsprinting paper substrate is 10g/m ²to 200g/m ², be 20g/m especially ²to 200g/m ², and be more particularly 40g/m ²to 200g/m ².The problem of existing ink is that it is tending towards print through in thinner newsprinting paper substrate, makes ink visible on the back side of substrate.It is found that, ink according to a first aspect of the invention can be printed well, has high light intensity, simultaneous minimization print through.

the container of ink

For the instrument that stores ink is provided, and for provide ink according to a first aspect of the invention, ink can be stored in vessel (vessel) to ink-jet printer.

Therefore,, in a third aspect of the present invention, a kind of vessel that hold ink are according to a first aspect of the invention provided.

Preferably suitable vessel, make it can be connected to ink-jet printer and are finally connected to printhead, thereby allow ink from vessel, derive through printer and arrive head.The example of suitable vessel comprises print cartridge, bottle, bucket, tank etc.Preferably, vessel have the contact that can be connected to printer, make not overflow and air can not be entrained into ink flow in the situation that, ink can be delivered to printing head at ink.

ink-jet printer

According to a forth aspect of the invention, provide a kind of ink-jet printer, this ink-jet printer comprises ink jet-print head and vessel according to a third aspect of the invention we.In print procedure, ink is flowed through conduit, passage, tubule etc. to ink jetting head from vessel.

Embodiment

example

Now by following instance, describe the present invention, wherein, except as otherwise noted, all umbers by weight.

1. the preparation of the granular solids of sealing

1.1 the preparation of dispersion agent (1)

Solution copolymerization by benzyl methacrylate and methacrylic acid is prepared dispersion agent, and its parts by weight are respectively 78.5 and 21.5.Dispersion agent is with the form isolation of solid body.This is dispersion agent (1).The acid number of dispersion agent (1) be 2.5 mmole acid groups/gram.

1.2 the preparation of dispersant solution (1)

The dispersion agent of 200 parts (1) is dissolved in water, to form 1000 parts, and take potassium hydroxide aqueous solution and neutralize to provide the aqueous solution that pH is approximately 9.This step produces and to comprise about 20%(weight) dispersant solution (1) of dispersion agent (1).

1.3 the preparation of mill base

1.3.1 black color paste (1)

Pigment powder (90 parts of charcoal blacks) and dispersant solution (1) (180 parts) is admixed together to form premixture.Water is joined to the appropriate viscosity to be provided for mixing and grinding in premixture in right amount.

Premixture is completely admixed together.After mixing, mixture is transferred to and is comprised in the bead mill that grinds pearl.Then mixture is ground to a few hours until arrive the particle size of the expectation that is about 110nm.Particle size is for passing through Malvern Zetasizer ^tMthe equal particle size of Z of measuring.

Then in the mixture from grinding, remove mill pearl.This step produces black color paste (1).

1.3.2 magenta mill base (1)

Except using the respective components in magenta pigment (85 parts of C.I. pigment 122) and dispersant solution (1) the broken pigment of (127.5 parts) replace black toner (1), by with the identical method preparation redness of black color paste (1) mill base (1).For magenta, pulverize pigment (1), grind and continue a few hours, until obtain the particle size that is about 120nm.Particle size is for passing through Malvern Zetasizer ^tMthe equal particle size of Z of measuring.This step produces magenta mill base (1).

1.3.3 yellow mill base (1)

Except using the respective components in yellow ultramarine (100 parts of C.I. Pigment Yellow 73s 74) and dispersant solution (1) the broken pigment of (250 parts) replace black toner (1), by preparing yellow mill base (1) with the identical method of black color paste (1).For yellow, pulverize pigment (1), grind and continue a few hours, until obtain the particle size that is about 120nm.Particle size is for passing through Malvern Zetasizer ^tMthe equal particle size of Z of measuring.This step produces yellow mill base (1).

1.3.4 blue-greenish colour mill base (1)

By pigment powder (the C.I. pigment Blue 15 of 150 parts: 3 powder) admixed together to form premixture with dispersant solution (1) (225 parts).Water is joined to the appropriate viscosity to be provided for mixing and grinding in premixture in right amount.

Premixture is completely admixed together.After mixing, mixture is transferred to and is comprised in the bead mill that grinds pearl.Then mixture is ground to a few hours until arrive the particle size of the expectation that is about 120nm.Particle size is for passing through Malvern Zetasizer ^tMthe equal particle size of Z of measuring.

Then in the mixture from grinding, remove mill pearl.This step produces blue-greenish colour mill base (1).

1.4 the preparation of the granular solids of sealing

By adding pure water, it is about 10%(weight that all mill bases in chapters and sections 1.3.1 to 1.3.4 are adjusted to solid content).

Then, use linking agent (purchased from the Denacol of Nagase ChemteX ^tMeX-321, epoxy equivalent (weight)=140, are after this abbreviated as EX-321) dispersion agent in crosslinked every kind of mill base.This step has been cross-linked the hydroxy-acid group in dispersion agent, and so encapsulated pigment.Crosslinking reaction is controlled in existence by a small amount of boric acid (purchased from Aldrich).By the mixture of describing being heated to the temperature of approximately 65 ℃ above, within 5 hours, cause crosslinking reaction.This step has been prepared a series of different granular solids of sealing, referring to the row 1 of table 1.

Table 1: crosslinked

The granular solids of sealing	Mill base (umber)	Linking agent (umber)	Boric acid umber
				EPS1	Blue-greenish colour mill base 1(3)	EX321(6.3)	2.78
EPS2	Magenta mill base 1(3)	EX321(3.57)	1.58
				EPS3	Yellow mill base 1(3)	EX321(4.9)	2.16
EPS4	Black color paste 1(3)	EX321(5.04)	2.23

1.5 the purifying of the granular solids of sealing

Above 1.4 in preparation the granular solids of sealing by the method for ultrafiltration, carry out purifying separately.The colo(u)rant dispersion thing that uses pure water diafiltration to seal.Then use the concentrated dispersion of sealing of ultra-filtration membrane, make its solid content get back to about 10%(weight) to 13%(weight).

2. the preparation of ink

By table 2 to the composition shown in table 4 is mixed with to ink component 1 to 11, wherein, the numeral of each composition all represents umber by weight.

Blending means for the preparation of ink is as follows:

Step 1-is by tensio-active agent Surfynol ^tM104E joins in the vessel that comprise ethylene glycol and stirs the mixture to form surfactant soln.

Step 2-joins other ink component the granular solids dispersion except sealing in surfactant soln.Implement to stir 10 minutes.This step forms liquid medium.

Step 3-joins the liquid medium forming in the granular solids dispersion of sealing above, stirs to guarantee the particulate stability in process for preparation simultaneously.The ink producing is further stirred 20 minutes or until obtains uniform ink.Can implement to stir by the mode of paddle stirrer.

table 2: ink 1 to 4

Component	?	Ink 1	Ink 2	Ink 3	Ink 4
						A. the granular solids of sealing	?	?	?	?	?
A. blue-greenish colour pigment	EPS1	4	?	?	?
						A. magenta pigment	EPS2	?	4	?	?

A. yellow ultramarine	EPS3	?	?	4	?
						A. black pigment	EPS4	?	?	?	4
B. glycerol	?	30	30	30	30
						C. ethylene glycol	?	18	18	18	18
D.2-pyrrolidone	?	5	5	5	5
						E. tensio-active agent	Surfynol ^RTM104E	0.8	0.8	0.8	0.8
F. polyoxyethylene glycol	Mn20000	0	0	0	0
						H. antimicrobial element	Proxel ^RTM?GXL	0.02	0.02	0.02	0.02
I. water	Deionized	46.18	46.18	46.18	46.18

table 3: ink 5 to 8

Component	?	Ink 5	Ink 6	Ink 7	Ink 8
						A. the granular solids of sealing	?	?	?	?	?
Blue-greenish colour pigment	EPS1	4	?	?	?
						Magenta pigment	EPS2	?	4	?	?
Yellow ultramarine	EPS3	?	?	4	?
						Black pigment	EPS4	?	?	?	4
B. glycerol	?	30	30	30	30
						C. ethylene glycol	?	18	18	18	18
D.2-pyrrolidone	?	5	5	5	5
						E. tensio-active agent	Surfynol ^RTM104E	0.8	0.8	0.8	0.8
F. polyoxyethylene glycol	Mn20000	1.87	1.73	1.27	1.47
						H. antimicrobial element	Proxel ^RTM?GXL	0.02	0.02	0.02	0.02
I. water	Deionized	44.31	44.45	44.91	44.71

table 4: ink 9 to 11

Component	?	Ink 9	Ink 10	Ink 11
					A. the granular solids of sealing	?	?	?	?
Blue-greenish colour	EPS1	?	?	?

Magenta	EPS2	?	?	?
					Yellow	EPS3	?	?	?
Black	EPS4	4	4	4
					B. glycerol	?	30	28	18
C. ethylene glycol	?	18	10	10
					D.2-pyrrolidone	?	0	5	5
E. tensio-active agent	Surfynol ^RTM104E	0.4	0.4	0.4
					F. polyoxyethylene glycol	Mn200	0	0	10
?	Mn10000	0	0.633	0.5
					H. antimicrobial element	Proxel ^RTM?GXL	0.02	0.02	0.02
I. water	Deionized	47.58	51.95	52.08

In each case, table 2 to the amount of the pigment of sealing (for example, blue-greenish colour, yellow, magenta and black) in table 4 all be take effective (or solid) amount of pigment for basic.Therefore, the pigment of 4 parts (using in ink 1 to 11) is 10%(weight corresponding to 40 parts of pigment contents) EPS dispersion.

Table 2 to 4 in, i) in the amount of water comprise the whole water coming from any ink component, such as the granular solids dispersion of sealing (approximately 90% water).Therefore, for example, in ink 9, the water of 47.58 parts comprises 36 parts of water from ESP4, remaining water (11.58 parts) for directly add to reach the amount of regulation.

3. the physical properties of ink

By pH meter, measure the pH value of ink 1 to 11.

Under the temperature condition of 30 ℃, the preferred method described in use is above measured the viscosity of ink 1 to 11.

At ink, under the condition of 25 ℃, use Kibron Aquapi measurement device surface tension.

The physical properties of ink is summarised in table 5.

table 5: the physical properties of ink of the present invention

Ink	Viscosity (mPa.s)	Surface tension (mN/m)	pH
				1	7.6	33.1	?
2	6.76	32.1	?
				3	7.23	31.8	?
4	7	31.3	?
				5	12.5	33.1	9.5
6	12.3	32	9.2
				7	11.8	31.8	9.3
8	11.4	31.3	9.3
				9	6.3	34.2	9.2
10	5.94	34.4	9.2
				11	5.89	35.1	9.2

4. spray ink Printing

It is found that, ink of the present invention can be realized good especially printing by ink-jet printer.Having observed remarkable droplet of ink forms and disperses.Contriver expects, the granular solids of sealing, produced remarkable drop form and dispersing characteristic for the preparation of the dispersion agent of the granular solids of sealing and the synergy of glycerol/glycol/water ink medium.

After printing for a long time, ink still can spray reliably.Ink can be printed on corrugated cardboard and newsprinting paper well.Ink provides the substrate perviousness of high light intensity, quick-drying and low degree.

Claims

1. an ink, comprises granular solids and the liquid medium sealed, wherein:

I) granular solids of sealing described in comprises the granular solids that uses crosslinked dispersion agent shell enclosure; And

II) described ink comprises following component:

A.0.1 part is to the granular solids of sealing described in 20 parts;

B.20 part to the glycerol of 40 parts;

C.1 part to the ethylene glycol of 30 parts;

D.0 part to the 2-Pyrrolidone of 20 parts;

E.0.01 part to the tensio-active agent of 3 parts;

F.0 part to the water-soluble polymers of 10 parts;

G.0 part to the polymer particles of 20 parts;

H.0 part to the biocide of 2 parts;

I.20 part to the water of 75 parts;

Wherein, all by weight, and the umber sum of component a to i is 100 parts to all umbers.

2. ink according to claim 1, wherein, described tensio-active agent has alkyne diol structure.

3. according to ink in any one of the preceding claims wherein, wherein, described tensio-active agent is 2,4,7,9-tetramethyl--5-decine-4,7-diol surfactant.

4. according to ink in any one of the preceding claims wherein, wherein, the amount of described ethylene glycol is 10 parts to 25 parts.

5. according to ink in any one of the preceding claims wherein, wherein, the amount of described water is 30 parts to 60 parts.

6. according to ink in any one of the preceding claims wherein, wherein, the amount of described 2-Pyrrolidone is 1 part to 10 parts.

7. according to ink in any one of the preceding claims wherein, wherein, the amount of described 2-Pyrrolidone is 2.5 parts to 7.5 parts.

8. according to ink in any one of the preceding claims wherein, wherein, described water-soluble polymers is polyoxyethylene glycol or comprises polyoxyethylene glycol.

9. ink according to claim 8, wherein, the amount of described polyoxyethylene glycol is that 0.1 part (weight) is to 3 parts (weight).

10. ink according to claim 9, wherein, the number-average molecular weight of described polyoxyethylene glycol is 5000 to 500000.

11. according to ink in any one of the preceding claims wherein, and wherein, the amount of described tensio-active agent is that 0.1 part (weight) is to 2 parts (weight).

12. according to ink in any one of the preceding claims wherein, and wherein, the amount of described tensio-active agent is that 0.1 part (weight) is to 1.5 parts (weight).

13. according to ink in any one of the preceding claims wherein, comprises that 0 part (weight) is to the polymer particles of 3 parts (weight).

14. according to ink in any one of the preceding claims wherein, and wherein, described dispersion agent is polymkeric substance, and by copolymerization component i at least) and ii) obtain and maybe can obtain described dispersion agent:

I) one or more (methyl) acrylate monomers of 70 parts to 95 parts, described in each, (methyl) acrylate monomer does not all have ionic group;

Ii) one or more (methyl) acrylate monomers of 5 parts to 30 parts, described in each, (methyl) acrylate monomer all has at least one ionic group;

15. according to ink in any one of the preceding claims wherein, and wherein, described dispersion agent is polymkeric substance, and by copolymerization component i at least) to iii) obtaining and maybe can obtain described dispersion agent:

I) one or more (methyl) acrylate monomers of 70 parts to 95 parts, described in each, (methyl) acrylate monomer does not all have ionic group, and described (methyl) acrylate monomer comprises at least 40 parts of benzyl methacrylates;

Ii) the methacrylic acid of 5 parts to 30 parts;

Iii) being no more than 5 parts, is more preferably one or more unsaturated vinyl monomers of 0 part, and described in each, unsaturated vinyl monomer all has polyethyleneoxy group;

Wherein, i) to umber sum be iii) 100, and all umber is all by weight.

16. according to ink in any one of the preceding claims wherein, wherein, and by dispersion agent shell described in the cross-linking reaction between carboxylic acid and epoxide group.

17. ink according to claim 1, comprise following component:

A.0.1 part is to the granular solids of sealing described in 10 parts;

B.20 part to the glycerol of 40 parts;

C.5 part to the ethylene glycol of 25 parts;

D.0 part to the 2-Pyrrolidone of 10 parts;

E.0.1 part to 2 parts 2,4,7,9-tetramethyl--5-decine-4,7-diol surfactant;

F.0 part to the polyoxyethylene glycol of 5 parts;

G.0 part to the polymer particles of 15 parts;

H.0 part to the biocide of 1 part;

I.35 part to the water of 55 parts;

Wherein, all by weight, and to select the amount of water to make the umber sum of component a to i be 100 parts to all umbers.

18. according to ink in any one of the preceding claims wherein, wherein, described granular solids for or comprise pigment.

19. according to ink in any one of the preceding claims wherein, comprises the optional ink component that is different from component a. to i., and all optional ink component are no more than 10 parts (weight).

20. according to ink in any one of the preceding claims wherein, and the viscosity of described ink is no more than 50mPa.s under the temperature condition of 30 ℃.

21. 1 kinds for arriving suprabasil technique according to ink print in any one of the preceding claims wherein.

22. techniques according to claim 21, wherein, implement to print by the mode of ink-jet printer.

23. techniques according to claim 22, wherein, are used one way ink-jet printer in one way, to implement spray ink Printing.

24. according to the technique described in any one in claim 21 to 23, and wherein, described substrate comprises porous surface, and the quality of described substrate is 40g/m ²to 800g/m ².

25. 1 kinds are held according to the vessel of the ink described in any one in claim 1 to 20.

26. 1 kinds of ink-jet printers that comprise ink jet-print head and vessel according to claim 25.